Oxidation of cyclic and aliphatic alcohols



United States Patent 3,165,554 Patented Jan. 12, 1965 lice 3 165 554 100 C. depending upon the cooling available, the rate 5 of introduction of chlorine and the hydrogen chloride OXIDATION OF CYCLIC AND ALIPHAHC acceptor employed. Preferably the temperature is from ALCOHOLS about 45 to about 60 c William H. Wineland, Midland, Micln, assignor to The h 1: Dow Chemical Company, Midland, Mich, a corporae Preferred hydtogen hade fien of Deaware nesium carbonate, calcium carbonate, Dolomite (mixtures No Drawing. Filed July 25, 1962, Ser. No. 212,451 of 3- 3) and the like Other useful p- 7 Claims. (Cl. 260-586) tors are the carbonates and bicarbonates of the alkali and alkaline earth metals and the hydroxides and oxides.

The present invention relates to a new and useful meth- 10 f th lk li th t l d i X for Oxidation of Secondary aleohels t0 their cone The amount of chlorine employed is from 0.25 to 1.2

Spending hetOIleS- More Particularly, the Present inveh' moles per mole of secondary alcohol and preferably from tion relates to the chlorine oxidation of cyclic and ali- 50 t 90 percent f th h ti l t react i h th phatic secondary alcohols which may be substituted with secondary l oh l,

an aromatic hydrocarbon radical of the benzene series S b t ti ll any Secondary l h l can b converted to their corresponding ketones at higher temperatures than t i col-respcmding k t Th one can convert th of r known With the result of improved Yields in aliphatic secondary alcohols such as the secondary aldesired product. kanols, e.g., 2-propanol, Z-butanol, 2pen-tanol, 3-pentanol,

The chlorine oxidation of a secondary alcohol to its Z-hexanQL 34 1, 2.1 t 1, 3-h t 1, 4-heptan0l, corresponding ketone at low temperatures is well known 2-octar1o l, 3-octanol, 4-octanol, Z-nonanol, 3-nonanol, 4. in the However, even at the low temperatures of nonanol, 5-nonano1, and the like to their corresponding to the Proeesses to date have usually been ketones and the cyclic alcohols, such as the secondary accompanied y low Yields and Conversions a further cycloalkanols, e.g., cyclohexanol, cyclopentanol, methyl wmpheeted y chlorination 0t some of the k tone, thus cyclohexanol, the cyclohexylcyclohexanols and the like even further reducing the Yields and conversions to 5 and the aryl substituted secondary aliphatic and cyclic Sh'ed Product At higher temperatures, above C': alcohols, such as a-hYdI'OXYCthYl benzenes and the like, the prior art teaches chlorination of the ketone is markedor 2 h 1 1 h 1 d th lik to th i correspond- 1y increased. ing ketones.

I11 accordance With the Present invention Secondary The following examples are illustrative of the present alcohols (i.e., aliphatic alcohols, cyclic alcohols, bicyclic 3O invention b are t t b construed as limiting; alcohols and phenyl substituted aliphatic and cyclic alcohols) are oxidized with chlorine or bromine or mixtures Example 1 thereof in the presence of a hydrogen halide acceptor I a 3090 1 -3 k Morton type fl k i d ith Such as cacoa, Mgcos miXthYeS thereof, Shch as a power stirrer (tru-bore; C blade), thermometer, reflux Dolomite, in an aqueous feeetteh medium at hlgh hcondenser and two extra coarse sintered glass gas inlet peratures, i.e. from about 0 to about 100 C. to obtain sparger tubes (33 Surface Per sparger) was charged, the corresponding unchlorinated ketone in good yields. 4()() grams cyclohexanol, 430 grams c co i i d), Good results are obtained when chlorine or bromine or and 1600 l water miX r thereof is p y in an amount of from The reaction flask was then immersed in a warm water to moles P mole of Secondary alcohol; When the 40 bath and the flask maintained at a temperature range hydrogen chloride acceptor is p y in from that of 57-60 C. At this temperature range 145 grams chloamount necessary to accept the theoretical chlorine of i were dd d t h rate of 058 gram per i t ith reaction to 12.5 percent in excess of the theoretical; and, f ll agitation Aft h completion f h hl i dwhen the aqueous Phase Contains from t0 4 times y dition the reaction was stirred for /2 hour and then steam Weight of Water based on the Weight of Secondary distilled from the reaction flask. A clear, water-white hol. When the lower water-alcohol ratio is employed, il i hi 429 grams was bt i d, Thi il l d the reaction is preferably carried out in a step-Wise manb i f -red had an assay of percent cyclohexanone ner, i.e., only a Portion Of the chlorine is added, the O1'- and percent cyclohexanol. ganics, acid and water are separated from the inorganic E l 2 7 salt and the chlorination repeated until the theoretical 50 mm? es chlorine has been added. In a similar manner varying the conditions the results The temperature of the reaction can range from 0 to indicated below were obtained.

Wt. of Wt. 0t Percent Per Per- Percent H O- cyclo- Gal. calcium Wt. of Temper- Wt. of Percent oi thecent cent 2-chloro- Ex cyclohexanol H2O carbonate C12 Chlorine ature rewet oil of theory oretical eyclocyclocyclo- Per- No. hexanol chargein charge incharge charged rate action distilled of oil re- 01 perhexahexahexacent Cl wt. ratio pounds in pounds in pounds zone, C. in pounds covered acleigd none n01 none 33 19.5 5- 2:1 200 50 188 110 1E2: fit: 212.0 96.8

1 Grams.

2 Synthetic mixture of 146 grams cyclohexanol-448 grams cyclohexanone to simulate proportional addition of chlorine and extraction of CaCOa.

3 Milliliters.

Example 8 In the manner of Example 1, employing the following amounts of reactants 455.6 grams octanol-2 (3.5 mol) 1500 ml. H

400 grams CaCO 255v grams chlorine In the manner of Example 1 employing the following amount of reactants 488 grams phenyl ethyl alcohol 1000 ml. H O

ml. CHZCIZ 450 grams CaCO and 295 grams of C1 added over a 4 hour minute period. at a temperature of 49 C. there was obtained 496.2 grams of wet oil analyzed by infra red about 96 percent acetophenone representing a 93 percent yield of product based on the starting alcohol.

Example 10 In a manner similar to Example 1 employing 526 grams 2-phenyl' cyclohexanol 1000 ml. H 0

1650 ml. CH Cl 350 grams CaCO and 220 grams C1 added over a 2 hour 23 minute period at 912 C. there was obtained a percent yield of Z-nhenyl cyclohexanone based on alcohol consumed.

This application is a continuation-in-part of my copending application Serial No. 844,208, filed October 5, 1959, now abandoned.

I claim: I

1. A method for converting a secondary alcohol to its corresponding ketone which comprises reacting in the aqueous phase a second alcohol selected from the group consisting of secondary alkanols, phenyl secondary alkanols, cycloalkanols, cyclohexylcyclohexanols and phenyl cycloalkanols with a halogen selected from the group consisting of chlorine and bromine in the presence of a hydrogen halide acceptor selected from the group consisting of the carbonates and bicarbonates of the alkali and alkaline earth metals and the hydroxides and oxides of alkaline earth metals and ammonia at a temperature of from 0 to C., the molar ratio of halogen to alcohol being between about 0.25 to 1.2.

2. The method as set forth in claim 1 wherein said reaction is carried out at a temperature of from 25 to 60 C.

3. The method as set forth in claim 1 wherein said halogen is chlorine.

4. The method as set forth in claim 2 wherein said halogen is chlorine.

5. The method as set forth in claim 4 wherein said alcohol is cyclohexanol.

6. The method as set forth in claim 4 wherein said alcohol is Z'phenyl cyclohexanol.

7. The method as set forth in claim 4 wherein said alcohol is l-phenyl ethanol.

References Cited in the file of this patent UNITED STATES PATENTS 2,444,924 Farkas et al July 13, 1948 

1. A METHOD FOR CONVERTING A SECONDARY ALCOHOL TO ITS CORRESPONDING KETON WHICH COMPRISES REACTING IN THE AQUEOUS PHASE A SECOND ALCOHOL SELECTED FROM THE GROUP CONSISTIG OF SECONDARY ALKANOLS, PHENYL SECONDARY ALKANOLS, CYCLOALKANOLS, CYCLOHEXYLCYCLOHEXANOLS AND PHENYL CYCLOALKANOLS WITH A HALOGEN SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE IN THE PRESENCE OF A HYDROGEN HALIDE ACCEPTOR SELECTED FROM THE GROUP CONSISTING OF THE CARBONATES AND BICARBONATES OF THE ALKALI AND ALKALINE EARTH METALS AND THE HYDROXIDES AND OXIDES OF ALKALINE EARTH METALS AND AMMONIA AT A TEMPERATURE OF FROM 0* TO 100*C., THE MOLAR RATIO OF HALOGEN TO ALCOHOL BEING BETWEEN ABOUT 0.25 TO 1.2. 